Porous ion-exchange resins with features of high selectivity, high capacity, fast adsorption kinetics and chemical stability over a wide pH range are attractive for extracting precious metals like copper and upcycling waste. In this study, porous glutaraldehyde-polyethyleneimine (GA-PEI) particulate resin was synthesised using diatomaceous earth (DE) particles as a bio-template. The crosslinking of PEI by GA was successfully conducted on the surface of DE. Removal of the template DE, merely by chemical etching with potassium hydroxide, resulted in the porous GA-PEI particulate resin. The resin showed excellent selectivity for copper ions in binding and recovery from solutions as complex as real legacy acid mine drainage liquid. The copper ion uptake capacity of the GA-PEI resin was determined to be >8 times greater than non-etched GA-PEI-DE particles. Under the investigated conditions, the GA-PEI resin showed higher selectivity to copper ions from real legacy acid mine drainage liquid compared to the commercial resins Purolite S930 Plus and Lewatit TP 220. Importantly, the absorbed copper ions could be released by simply adjusting pH of the solution to 1. For uptake from acid mine drainage liquid at pH 4 and elution at pH 1, purer copper solutions were achieved with GA-PEI compared to Purolite S930 Plus or Lewatit TP 220 following two cycles of iteration. The results indicate the great potential for using the porous GA-PEI resin in copper extraction under real-world conditions.